[go: up one dir, main page]

CN101538338A - Epoxidation method of gel-free double bond-contained polymer - Google Patents

Epoxidation method of gel-free double bond-contained polymer Download PDF

Info

Publication number
CN101538338A
CN101538338A CN200910111455A CN200910111455A CN101538338A CN 101538338 A CN101538338 A CN 101538338A CN 200910111455 A CN200910111455 A CN 200910111455A CN 200910111455 A CN200910111455 A CN 200910111455A CN 101538338 A CN101538338 A CN 101538338A
Authority
CN
China
Prior art keywords
polymer
epoxidation
gel
double bond
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN200910111455A
Other languages
Chinese (zh)
Other versions
CN101538338B (en
Inventor
林国良
吴维芬
余谋发
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiamen University
Original Assignee
Xiamen University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiamen University filed Critical Xiamen University
Priority to CN200910111455XA priority Critical patent/CN101538338B/en
Publication of CN101538338A publication Critical patent/CN101538338A/en
Application granted granted Critical
Publication of CN101538338B publication Critical patent/CN101538338B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

无凝胶含双键聚合物的环氧化方法，涉及一种聚合物的环氧化方法，尤其是涉及一种可避免环氧化反应中出现凝胶，改善环氧化产物溶解性能，解决含双键聚合物环氧化产物工业化生产中难题的无凝胶含双键聚合物的环氧化方法。提供一种改进的无凝胶含双键聚合物的环氧化方法。将聚合物溶解在有机溶剂中得聚合物溶液，加入季铵盐和甲酸，搅拌得溶液A；将过氧化氢加入溶液A中，先保温反应至少1h，再升温反应得反应产物，清洗后，分出有机层，减压除去溶剂，即可制得环氧化的无凝胶含双键聚合物。通过添加一种季铵盐或几种季铵盐的复配物，避免在环氧化反应过过程中出现凝胶化现象，使环氧化反应顺利进行，环氧化产物具有良好的溶解性能。

The epoxidation method of a gel-free double bond-containing polymer relates to an epoxidation method of a polymer, especially relates to an epoxidation method that can avoid the occurrence of gel in the epoxidation reaction, improve the solubility of the epoxidation product, and solve the problem of The invention relates to a gel-free epoxidation method of a double bond-containing polymer which is difficult in the industrial production of a double bond-containing polymer epoxidation product. An improved gel-free epoxidation method for polymers containing double bonds is provided. Dissolve the polymer in an organic solvent to obtain a polymer solution, add quaternary ammonium salt and formic acid, and stir to obtain a solution A; add hydrogen peroxide to the solution A, first heat the reaction for at least 1 hour, then heat up the reaction to obtain a reaction product, after cleaning, The organic layer is separated, and the solvent is removed under reduced pressure to obtain an epoxidized gel-free polymer containing double bonds. By adding a quaternary ammonium salt or a compound of several quaternary ammonium salts, it can avoid gelation during the epoxidation reaction, so that the epoxidation reaction can proceed smoothly, and the epoxidation product has good solubility .

Description

The epoxidizing method of gel-free double bond-contained polymer
Technical field
The present invention relates to a kind of epoxidizing method of polymkeric substance, especially relate to a kind of gel of can avoiding occurring in the epoxidation reaction, improve the solubility property of epoxidation product, solve the epoxidizing method of the gel-free double bond-contained polymer of an important difficult problem in the double bond-contained polymer epoxidation product suitability for industrialized production.
Background technology
Double bond-contained polymer is the important polymkeric substance of a class, and they normally are that monomer makes by homopolymerization or copolymerization with the conjugated diene.This base polymer has elasticity preferably usually, can be used as elastomerics and uses.But because this class material polarity is poor, make its oil-proofness, cohesiveness and ventilation property relatively poor, limited the Application Areas of double bond-contained polymer.In order to improve the polarity of this base polymer, can be when polymerization by introducing polar group with the specific polarity monomer copolymerization, but because specific polarity monomer kind is few, the price height has limited the application of this method.Another kind method is to finish the back in polymerization to introduce polar group by chemical modification in polymkeric substance, and this method is simple to operate, can require to introduce specific group according to reality, therefore has extremely widely and uses.
Two keys are easy to be oxidized to epoxy group(ing) under the effect of suitable oxidizing agent in the polymkeric substance, this not only can realize the polar of polymkeric substance, can also in polymkeric substance, introduce the two higher epoxy group(ing) of key of reactivity ratio, give polymkeric substance new reactivity worth, double bond-contained polymer is converted into a kind of functional materials, so the epoxidation modification of double bond-contained polymer has important use value.Research has had 40 years history to the double bond-contained polymer epoxidizing method, but up to the present also rests on the laboratory study stage, does not begin large-scale commercial applications production.The major cause of restriction large-scale industrial production is to be attended by serious crosslinking side reaction in epoxidation reaction, has influenced the epoxidation product solubility property, produces gel phenomenon when serious in reaction.Simultaneously, the measure of existing inhibition crosslinking side reaction also tends to epoxidation reaction is caused detrimentally affect, so the control of reaction conditions is very difficult.
The peroxidation formic acid that hydrogen peroxide and formic acid reaction in generate is a kind of important epoxidation reagent, and it has simple to operate, characteristics such as raw material is cheap, accessible double bond conversion rate height.But when finding to use this epoxidation systems epoxidation double bond-contained polymer in actual applications, reaction 2～3h afterreaction system will gel occur and reaction can't be carried out.Udipi (U.S. Pat 4 131 725) proposes the unit acid substitution formic acid with part carbon number 2～9, can effectively suppress crosslinking side reaction.But this innovative approach meeting makes epoxidation reaction speed slack-off, in order to reach high epoxidation transformation efficiency, just must prolong the reaction times, increases the consumption of hydrogen peroxide, has influenced the economic benefit of epoxidation technique.
Summary of the invention
The object of the present invention is to provide a kind of epoxidizing method of improved gel-free double bond-contained polymer.
Technical scheme of the present invention is to add a small amount of quaternary ammonium salt in the system that is epoxidation reagent with hydrogen peroxide and formic acid mixtures, to improve epoxidation reaction stability, avoid the generation of gel phenomenon, can not produce tangible detrimentally affect simultaneously epoxidation reaction.
The present invention includes following steps:
1) with polymer dissolution in organic solvent, polymers soln, in polymers soln, add quaternary ammonium salt and formic acid, stir, solution A;
2) hydrogen peroxide is added in the solution A, first insulation reaction is 1h at least, and temperature reaction again gets reaction product;
3) with after the reaction product cleaning, tell organic layer, removal of solvent under reduced pressure can make epoxidised gel-free double bond-contained polymer.
In step 1), described organic solvent is selected from least a in toluene, hexanaphthene, 1,2 ethylene dichloride, parachlorotoluene, trichloromethane, the dimethylbenzene etc.; The mass percent concentration of described polymers soln can be 10%～55%, is preferably 10%～35%; Press mass ratio, polymkeric substance: quaternary ammonium salt: formic acid is preferably 100: (0.3～5): (0.5～10);
Described quaternary ammonium salt is selected from least a quaternary ammonium salt that has in the following formula structure, as the anti-gel protective material of epoxidation reaction:
Figure A20091011145500051
R in structural formula (1) 1, R 2, R 3, R 4Be carbon number 1～12 alkyl, benzyl; R in the structural formula (2) (3) 1, R 2Be alkyl, phenyl, the benzyl of carbon number 1～12, and R 3, R 4, R 5Except being the alkyl, benzyl, phenyl of carbon number 1～12, can also be H; R in the structural formula (4) (5) 1Be alkyl, benzyl, the phenyl of carbon number 1～12, and R 2, R 3, R 4, R 5, R 6Can be H, the alkyl of carbon number 1～12, phenyl, benzyl.
In step 2) in, the temperature of described insulation reaction is preferably 30～40 ℃, and the temperature of described temperature reaction is preferably 60～70 ℃, and the time of temperature reaction is preferably 4～8h; Press mass ratio, solution A: hydrogen peroxide is preferably 100: (10～80), by mass percentage, the concentration of hydrogen peroxide is preferably 10%～30%.
Described double bond-contained polymer is meant with the conjugated diene to be homopolymerization of monomer synthetic or copolymerization superpolymer, and its molecular weight is 800～10 6Between.
The present invention adds a small amount of quaternary ammonium salt based on traditional epoxidation technique prescription in system, can play stabilization to reaction system viscosity, avoids gel phenomenon occurring in epoxidation reaction, and epoxidation reaction is carried out smoothly.The quaternary ammonium salt that adds is little to the epoxidation reaction influence, and epoxidation reaction can be carried out with speed of response faster.The epoxidation product that makes in this way has the oxirane value height, and the extraction residual rate is low, and solubility property is good, the productive rate advantages of higher, and the epoxidation product double bond conversion rate is more than 60%, and wherein oxirane value is not less than 0.46mol/100g; The extraction residual rate is not more than 4.5%; The epoxidation product productive rate is more than 55%.These advantages make the industrialization of epoxidised double bond-contained polymer product have appreciable prospect.
Description of drawings
Fig. 1 is the influence of organic salt to reaction system viscosity.In Fig. 1, X-coordinate is reaction times (h), and ordinate zou is viscosity (cps); ■ is for adding organic salt system, ● for adding organic salt system; Traditional system gel occurs behind reaction 2～3h, so innumerable strong point behind the 3h.
Embodiment
Following examples will the present invention is further illustrated in conjunction with the accompanying drawings, is noted that the present invention is not limited to following each specific embodiment.
Embodiment 1
Dissolve styrene-butadiene rubber(SBR) (Mn=3.5 * 10 with toluene solvant 5) formation 15%wt styrene-butadiene rubber(SBR) solution.Get the above-mentioned styrene-butadiene rubber(SBR) solution of 100g, add 0.3g benzyl trimethyl ammonium chloride, 7.6mL formic acid again, be warmed up to 40 ℃ behind the formation homogeneous solution, slowly be added dropwise to 10mL30% (v/v) hydrogen peroxide again.Be incubated 1h down at 40 ℃ earlier, be warmed up to 60 ℃ of reaction 5h again.Reaction finishes the back with deionized water wash 4 times, tells organic layer with separating funnel, decompression remove toluene get final product epoxidation styrene-butadiene rubber(SBR).
Epoxidation styrene-butadiene rubber(SBR) double bond conversion rate 76.3%, the extraction residual rate is 1.34%.
Embodiment 2
Dissolve cis-1,4-polybutadiene rubber (Mn=1.1 * 10 with hexanaphthene 5) formation 10%wt cis-1,4-polybutadiene rubber solution.Get the above-mentioned solution of 100g, add 1.2g chlorination N-methylimidazole, 4.5mL formic acid again, be warmed up to 40 ℃ behind the formation homogeneous solution, slowly be added dropwise to 20mL15% (v/v) hydrogen peroxide again.At 40 ℃ of insulation 2h, be warmed up to 65 ℃ of reaction 4h again.Reaction finishes the back with deionized water wash 4 times, tells organic layer with separating funnel, decompression remove hexanaphthene get final product the epoxidation cis-1,4-polybutadiene rubber.
Epoxidation cis-1,4-polybutadiene rubber double bond conversion rate is 81.3%, and the extraction residual rate is 3.26%.
Embodiment 3
With 1,2 ethylene dichloride dissolving natural rubber (Mn=1.27 * 10 6) form the solution of 20%wt.Get the above-mentioned solution of 100g then, add 0.4g chlorination N-dimethylbenzimidazole, 3.4mL formic acid again, be warmed up to 40 ℃ behind the formation homogeneous solution, slowly be added dropwise to 22mL15% (v/v) hydrogen peroxide.At 40 ℃ of insulation 1h, be warmed up to 65 ℃ of reaction 6h again.Reaction finishes the back with deionized water wash 3 times, tells organic layer with separating funnel, decompression remove hexanaphthene get final product epoxy natural rubber.
The epoxy natural rubber double bond conversion rate is 85.4%, and the extraction residual rate is 2.83%.
Embodiment 4
With parachlorotoluene dissolving SIS block polymer (Mn=1.27 * 10 5) formation 17wt% solution.Get above-mentioned solution 100g then, add 0.8g bromination N-ethylpyridine again, 6.5mL formic acid is warmed up to 40 ℃ behind the formation homogeneous solution, slowly is added dropwise to 17mL15% (v/v) hydrogen peroxide.At 40 ℃ of insulation 1.5h, be warmed up to 75 ℃ of reaction 4h again.Reaction finishes the back with deionized water wash 2 times, tells organic layer with separating funnel, decompression remove hexanaphthene get final product epoxy SIS.
Epoxidation SIS double bond conversion rate is not less than 81.2%, and the extraction residual rate is not higher than 3.67%.
Embodiment 5
With toluene and the partially hydrogenated SBS block polymer of trichloromethane mixed solvent compound (1: 1 V/V) dissolving (Mn=2.7 * 10 5) formation 10%wt solution.Four octyl group ammonium chlorides=1: 2 (W/W)), 8.7mL formic acid get the above-mentioned solution of 100g then, add the composite quaternary ammonium salt of 0.6g (chlorination N-picoline:, be warmed up to 40 ℃ after forming homogeneous solution, slowly be added dropwise to 12mL30% (v/v) hydrogen peroxide more again.At 40 ℃ of insulation 1h, be warmed up to 55 ℃ of reaction 8h again.Reaction finishes the back with deionized water wash 4 times, tells organic layer with separating funnel, decompression remove hexanaphthene get final product epoxidation partial hydrogenation SBS.
The epoxidation product double bond conversion rate is 63.6%, and the extraction residual rate is 1.34%.
Embodiment 6
With 1, the 2-ethylene dichloride is dissolution with solvents EPDM rubber (Mn=2.13 * 10 5) formation 10%wt solution.Get above-mentioned solution 100g then, add 0.4g chlorination N-methyl benzo pyridine, 4mL formic acid again, be warmed up to 40 ℃ behind the formation homogeneous solution, slowly be added dropwise to 13mL15% (v/v) hydrogen peroxide again.At 40 ℃ of insulation 1h, be warmed up to 65 ℃ of reaction 5h again.Reaction finishes the back with deionized water wash 4 times, tells organic layer with separating funnel, decompression remove hexanaphthene get final product epoxidation EPDM.
The epoxidation product double bond conversion rate is 61.3%, and the extraction residual rate is 1.54%.
Embodiment 7
With dimethylbenzene is dissolution with solvents liquid cis butadiene (Mn=2000), forms 45%wt solution.Four octyl group brometo de amonios=2: 3 (W/W)), 5mL formic acid get above-mentioned solution 100g, add the composite quaternary ammonium salt of 0.56g (Tetrabutyl amonium bromide:, be warmed up to 40 ℃ after forming homogeneous solution, slowly be added dropwise to 27mL30% (v/v) hydrogen peroxide more again.At 40 ℃ of insulation 1h, be warmed up to 65 ℃ of reaction 4h again.Reaction finishes the back with deionized water wash 4 times, tells organic layer with separating funnel, removal of solvent under reduced pressure get final product the epoxidized liquid cis-1,4-polybutadiene rubber.
The epoxidation product double bond conversion rate is more than 75%, and the extraction residual rate is not higher than 3.18%.
Embodiment 8
With toluene and hexanaphthene mixing solutions (1: 1 (V/V)) dissolving liquid acrylonitrile butadiene rubber (Mn=1000), form 40%wt liquid acrylonitrile butadiene rubber solution.Bromination N-methylimidazole=3: 1 (W/W)), 5mL formic acid get 100g liquid acrylonitrile butadiene rubber solution, add the composite quaternary ammonium salt of 0.3g (4 bromide:, be warmed up to 40 ℃ after forming homogeneous solution, slowly be added dropwise to 20mL15% (v/v) hydrogen peroxide more again.At 40 ℃ of insulation 1h, be warmed up to 65 ℃ of reaction 4h again.Reaction finishes the back with deionized water wash 4 times, tells organic layer with separating funnel, removal of solvent under reduced pressure get final product the epoxidized liquid paracril.
The epoxidation product double bond conversion rate is more than 81.4%, and it is 3.18% that the extraction residual rate is not higher than.
Described double bond-contained polymer strength of solution is between 10%～55% (wt).The solvent that is fit to be used as epoxidation reaction organic phase medium comprises naphthenic hydrocarbon, aromatic hydrocarbons, chloroparaffin, chloro naphthenic hydrocarbon, chlorinated aromatic hydrocarbons and their mixture.Can according to similarly mix, polar principle, solubility parameters principle from above-mentioned solvent, select can dissolve polymer solvent.
The variation of interpolation quaternary ammonium salt afterreaction system viscosity is as shown in Figure 1 in epoxidation systems. and as can be seen from the figure organic salt plays stabilization to the viscosity of reaction system, and the viscosity of system only has slight increase before and after the reaction.Sharply do not rise and do not add organic salt system viscosity, will produce gel behind reaction 2～3h.This shows that quaternary ammonium salt is splendid to the epoxidation reaction stabilising effect.

Claims (9)

1.无凝胶含双键聚合物的环氧化方法，其特征在于包括以下步骤：1. the epoxidation method of non-gel containing double bond polymer is characterized in that comprising the following steps: 1)将聚合物溶解在有机溶剂中，得聚合物溶液，在聚合物溶液中加入季铵盐和甲酸，搅拌，得溶液A；1) dissolving the polymer in an organic solvent to obtain a polymer solution, adding a quaternary ammonium salt and formic acid to the polymer solution, and stirring to obtain a solution A; 2)将过氧化氢加入溶液A中，先保温反应至少1h，再升温反应，得反应产物；2) Add hydrogen peroxide into solution A, first keep warm for at least 1 hour, and then heat up to react to obtain a reaction product; 3)将反应产物清洗后，分出有机层，减压除去溶剂，即可制得环氧化的无凝胶含双键聚合物。3) After the reaction product is washed, the organic layer is separated, and the solvent is removed under reduced pressure to obtain an epoxidized gel-free double bond-containing polymer. 2.如权利要求1所述的无凝胶含双键聚合物的环氧化方法，其特征在于在步骤1)中，所述有机溶剂选自甲苯、环己烷、1，2二氯乙烷、对氯甲苯、三氯甲烷、二甲苯中的至少一种。2. the epoxidation method of non-gel containing double bond polymer as claimed in claim 1, is characterized in that in step 1), described organic solvent is selected from toluene, hexanaphthene, 1,2 ethylene dichloride at least one of alkane, p-chlorotoluene, chloroform, and xylene. 3.如权利要求1所述的无凝胶含双键聚合物的环氧化方法，其特征在于在步骤1)中，所述聚合物溶液的质量百分比浓度为10％～55％。3. The method for epoxidation of a gel-free double bond-containing polymer according to claim 1, characterized in that in step 1), the mass percent concentration of the polymer solution is 10% to 55%. 4.如权利要求1所述的无凝胶含双键聚合物的环氧化方法，其特征在于在步骤1)中，按质量比，聚合物∶季铵盐∶甲酸为100∶(0.3～5)∶(0.5～10)。4. the epoxidation method of non-gel containing double bond polymer as claimed in claim 1 is characterized in that in step 1), by mass ratio, polymer: quaternary ammonium salt: formic acid is 100: (0.3～ 5): (0.5～10). 5.如权利要求1所述的无凝胶含双键聚合物的环氧化方法，其特征在于在步骤1)中，所述季铵盐选自具有下式结构中的至少一种季铵盐，作为环氧化反应的抗凝胶保护剂：5. the epoxidation method of non-gel containing double bond polymer as claimed in claim 1 is characterized in that in step 1), the quaternary ammonium salt is selected from at least one quaternary ammonium in the following formula structure Salt, as a gel protectant against epoxidation reactions:
Figure A2009101114550002C1
Figure A2009101114550002C1
 在结构式(1)中R1、R2、R3、R4为碳数1～12烷基、苄基；结构式(2)(3)中R1、R2为碳数1～12的烷基、苯基、苄基，而R3、R4、R5除了是碳数1～12的烷基、苄基、苯基外，还是H；结构式(4)(5)中R1为碳数1～12的烷基、苄基、苯基，而R2、R3、R4、R5、R6为H、碳数1～12的烷基、苯基、苄基。In structural formula (1), R 1 , R 2 , R 3 , and R 4 are alkyl groups and benzyl groups with 1 to 12 carbons; in structural formulas (2) and (3), R 1 and R 2 are alkyl groups with 1 to 12 carbons. base, phenyl, benzyl, and R 3 , R 4 , R 5 are not only alkyl, benzyl, and phenyl with 1 to 12 carbons, but also H; in structural formula (4) (5), R 1 is carbon Alkyl, benzyl, or phenyl with 1 to 12 carbons, and R 2 , R 3 , R 4 , R 5 , and R 6 are H, alkyl, phenyl, or benzyl with 1 to 12 carbons. 6.如权利要求1所述的无凝胶含双键聚合物的环氧化方法，其特征在于在步骤2)中，所述保温反应的温度为30～40℃，所述升温反应的温度为60～70℃，升温反应的时间为4～8h。6. The epoxidation method of gel-free double bond-containing polymer as claimed in claim 1, characterized in that in step 2), the temperature of the heat preservation reaction is 30～40°C, and the temperature of the temperature rise reaction The temperature is 60-70°C, and the heating reaction time is 4-8 hours. 7.如权利要求1所述的无凝胶含双键聚合物的环氧化方法，其特征在于在步骤2)中，按质量比，溶液A∶过氧化氢为100∶10～80。7. The epoxidation method of gel-free polymer containing double bonds as claimed in claim 1, characterized in that in step 2), by mass ratio, solution A: hydrogen peroxide is 100: 10～80. 8.如权利要求1所述的无凝胶含双键聚合物的环氧化方法，其特征在于在步骤2)中，按质量百分比，过氧化氢的浓度为10％～30％。8. The epoxidation method of a gel-free double bond-containing polymer as claimed in claim 1, characterized in that in step 2), the concentration of hydrogen peroxide is 10% to 30% by mass percentage. 9.如权利要求1所述的无凝胶含双键聚合物的环氧化方法，其特征在于所述含双键聚合物是指以共轭二烯烃为单体合成的均聚或共聚高聚物，其分子量为800～106。9. the epoxidation method of non-gel-containing double-bond polymer as claimed in claim 1, is characterized in that described double-bond-containing polymer refers to the homopolymerization or copolymerization high-polymerization that takes conjugated diene as monomer synthesis A polymer with a molecular weight of 800-10 6 .
CN200910111455XA 2009-04-09 2009-04-09 Epoxidation method of gel-free double bond-contained polymer Expired - Fee Related CN101538338B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN200910111455XA CN101538338B (en) 2009-04-09 2009-04-09 Epoxidation method of gel-free double bond-contained polymer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN200910111455XA CN101538338B (en) 2009-04-09 2009-04-09 Epoxidation method of gel-free double bond-contained polymer

Publications (2)

Publication Number Publication Date
CN101538338A true CN101538338A (en) 2009-09-23
CN101538338B CN101538338B (en) 2011-11-09

Family

ID=41121743

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200910111455XA Expired - Fee Related CN101538338B (en) 2009-04-09 2009-04-09 Epoxidation method of gel-free double bond-contained polymer

Country Status (1)

Country Link
CN (1) CN101538338B (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105860175A (en) * 2015-01-23 2016-08-17 中国石油天然气股份有限公司 Preparation method of tread rubber containing epoxidized styrene-butadiene rubber
CN105949353A (en) * 2016-05-25 2016-09-21 付文 Method for preparing epoxidized SBS (styrene butadiene styrene)
CN112250776A (en) * 2020-08-13 2021-01-22 沧州信联化工有限公司 Tetramethyl ammonium hydroxide catalytic thermoplastic material and preparation method thereof
WO2021105037A1 (en) 2019-11-28 2021-06-03 Evonik Operations Gmbh Polyether-modified polybutadienes and process for the preparation thereof
EP4047031A1 (en) 2021-02-17 2022-08-24 Evonik Operations GmbH Amino-functional polybutadienes with comb-resistant polyether remnants and method for their production
EP4095165A1 (en) 2021-05-27 2022-11-30 Evonik Operations GmbH Polyester-polyether-modified polybutadiene and method for producing the same
WO2022248267A1 (en) 2021-05-27 2022-12-01 Evonik Operations Gmbh Hydrogenated polyether-modified amino-functional polybutadienes and process for their preparation
WO2022248266A1 (en) 2021-05-27 2022-12-01 Evonik Operations Gmbh Hydrogenated polyether-modified polybutadienes and process for their preparation
CN117362803A (en) * 2023-10-30 2024-01-09 广东诚和信新材料有限公司 Flame-retardant PE composite material

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105860175A (en) * 2015-01-23 2016-08-17 中国石油天然气股份有限公司 Preparation method of tread rubber containing epoxidized styrene-butadiene rubber
CN105949353A (en) * 2016-05-25 2016-09-21 付文 Method for preparing epoxidized SBS (styrene butadiene styrene)
WO2021105037A1 (en) 2019-11-28 2021-06-03 Evonik Operations Gmbh Polyether-modified polybutadienes and process for the preparation thereof
US12139561B2 (en) 2019-11-28 2024-11-12 Evonik Operations Gmbh Polyether-modified polybutadienes and processes for preparation thereof
CN112250776A (en) * 2020-08-13 2021-01-22 沧州信联化工有限公司 Tetramethyl ammonium hydroxide catalytic thermoplastic material and preparation method thereof
CN112250776B (en) * 2020-08-13 2022-07-22 沧州信联化工有限公司 Tetramethyl ammonium hydroxide catalytic thermoplastic material and preparation method thereof
WO2022175140A1 (en) 2021-02-17 2022-08-25 Evonik Operations Gmbh Aminofunctional polybutadiene with lateral polyether radicals and method for producing same
EP4047031A1 (en) 2021-02-17 2022-08-24 Evonik Operations GmbH Amino-functional polybutadienes with comb-resistant polyether remnants and method for their production
EP4095165A1 (en) 2021-05-27 2022-11-30 Evonik Operations GmbH Polyester-polyether-modified polybutadiene and method for producing the same
WO2022248267A1 (en) 2021-05-27 2022-12-01 Evonik Operations Gmbh Hydrogenated polyether-modified amino-functional polybutadienes and process for their preparation
WO2022248266A1 (en) 2021-05-27 2022-12-01 Evonik Operations Gmbh Hydrogenated polyether-modified polybutadienes and process for their preparation
US12104003B2 (en) 2021-05-27 2024-10-01 Evonik Operations Gmbh Polyester-polyether-modified polybutadienes and processes for preparation thereof
CN117362803A (en) * 2023-10-30 2024-01-09 广东诚和信新材料有限公司 Flame-retardant PE composite material
CN117362803B (en) * 2023-10-30 2024-04-02 广东诚和信新材料有限公司 Flame-retardant PE composite material

Also Published As

Publication number Publication date
CN101538338B (en) 2011-11-09

Similar Documents

Publication Publication Date Title
CN101538338A (en) Epoxidation method of gel-free double bond-contained polymer
CN104736574B (en) The manufacture method and hydrogenation catalyst composition of hydrogenation catalyst composition
CN102382223A (en) Method for preparing brominated butyl rubber
CN103865262B (en) Application of Hyperbranched Polymer in Waterproof Membrane
CN104448059B (en) High-cis-Isosorbide-5-Nitrae content epoxy terminal hydroxyl polybutadiene liquid rubber and preparation method thereof
CN102532379B (en) Polymerization method for preparing rare earth isoprene rubber
CN104231118B (en) Hydrogenation hydroxyl terminated butyl nitrile (HTBN) rubber and preparation method thereof
CN103159963B (en) Preparation method of high-performance powdered nitrile rubber
EP3401364B1 (en) Asphalt modifier and asphalt composition comprising same
BR112020000244A2 (en) star-branched diene rubber
CN105622784B (en) Hydroxy functionalized polyethylene and preparation method thereof
CN108102008A (en) A kind of preparation method of epoxidation terminal hydroxyl polybutadiene liquid rubber
WO2018038460A1 (en) Method for producing vinylidene chloride
CN103865281A (en) Asphalt viscoelasticity modifier and preparation method thereof
CN102766156B (en) The preparation method of tetramethyl divinyl disilazane
JP2012500310A5 (en)
CN108203486A (en) Preparation method of environment-friendly oil-extended styrene-butadiene rubber
CN110540608B (en) Method for preparing hydrogenated diene based nanoemulsions and use of gemini surfactants
CN102634037A (en) Long chain branched styrenic thermoplastic elastomer polymer and preparation method thereof
JP5785191B2 (en) High CIS polybutadiene rubber in harmless solvent and process for preparing the same
CN108948247B (en) Low-molecular-weight epoxy-terminated polybutadiene, and preparation method and application thereof
CN108102009A (en) A kind of epoxidation terminal hydroxyl polybutadiene liquid rubber
CN106397635B (en) A kind of siliceous alternately EP rubbers and preparation method thereof of bio-based
CN104292395A (en) Macromolecular polymerized phenol modified polydicyclopentadiene material and preparation method thereof
CN107200794B (en) A kind of method of hydrotreating of NBR latex

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20111109

Termination date: 20150409

EXPY Termination of patent right or utility model